Process for dyeing paper employing metalized dyestuffs containing diethylene triamine



United States Patent Office 3,537,807

Patented Nov. 3, 1970 Diethylene triamine appears to be quite unique in this PROCESS FOR DPER EMPLOYING action of overcoming graniting in dyeing paper with this class of dyestufls since if an equivalent amount of closely S CONTAINING related chemical compounds, ethylene diamine or tri- Clemens Streck, Loudonville, N.Y., assignor to GAF 5 i tetramine is prefsent in thfi dyebath than granit- Corporation, New York, N.Y., a corporation of Delamg not reduced matenanyware No Drawing. Filied 1;lih1916/'L,6Ser. No. 622,940 DESCRIPTION OF THE PREFERRED nt. D EMBODIMENTS U.S. Cl. 8-7 4 Claims 10 The dyestuifs of the formula given above which are included within the scope of this invention are known ABSTRACT OF THE DISCLOSURE dyes and may be produced by tetrazotizing one molar Paper is dyed with dyestuffs of the formula: proportion of o-dianisidine or o,o'-dihydroxybenzidine OCu-O OCu-O X l l I aHh 3 wherein n is 1-2, and X is hydrogen, chlorine or NH R, and coupling under alkaline conditions With approx- Wherein R is hydrogen, lower alkyl, benzyl, aryl or acyl, irnately 2 moles of a coupler having the formula: to which there has been added 5-20 parts of diethylene OH triamine and preferably l0-30 parts of (A) dialkali r'netal X phosphate and/ or (B) hexamethylene tetramine for 100 parts of dyestuflf to obtain an even dyeing of true shade.

BACKGROUND OF INVENTION 6,

This invention relates to the process of dyeing paper. wherein X and n have the same definitions as above and In the dyeing of paper employing dyestufis of the folcoppering by any known method used to copper o,o'-dilowing general formula: hydroxy type azo dyes.

O--Cu0 OCu--O X X wherein n is 1-2, and X is hydrogen, chlorine or -NHR, Such couplers are exemplified by: wherein R is hydrogen, lower alkyl, benzyl, aryl or acyl, a great deal of graniting (uneven splotchy dyeing having laphthol-3-sulfonrc ac d, a granite-like appearance) frequently occurs. Such dye- 1'I1aPhth01-4-Su1f0nlc field,

l-naphthol-S-sulfonic acid, S-amino-l-naphthol-3-sulfonic acid,

ings are not desirable and attempts to overcome this difficulty have not been wholly successful.

6-amino-1-naphthol-3-sulfonic acid,

SUMMARY 6-methylamino-l-naphthol-S-sulfonic acid, I have found that if a small amount, preferably from 6-benzylamino-1-naphthol-3-sulfonic acid, 5-20 parts by weight of diethylene triamine, is present in 6-anilino-1-naphthol-3-sulfonic acid, the dyebath per 100 parts of dyestutf, this problem of 6-p-anisidin0-l-naphthol-3-sulf0nic a id,

graniting is largely overcome. I have also found that if 7 a i o-l a hth l 3 ulf i acid, 10-30 parts by Weight of a stabilizing material selected 7 ili l hth l 3 lf i acid, from the group consisting of (A) hexamethylene tetra- 8 i 1 hth l 3 lf i acid mine and (B) dialkali metal phosphate such as dilithium, disodium or dipotassium phosphate, or a mixture of (A) and (B) is present in the dyebath per 100 parts of dyestuif, decomposition of the dyestutf and resultant tendency to give a redder shade during dyeing of the paper 22K2 gi g g f ;i acld web is very substantially inhibited. h 1 a f While the diethylene triamine, and also the hexamethyll'nap t 0 omc acld 60 8-anilino-l-naphthol-3-sulfonic acid,

S-amino-l-naphthol-S-sulfonic acid, 8-anilino-l-naphthol-S-sulfonic acid,

ene tetramine and/or dialkali metal phosphate if used, f a may be added to the dyebath, it is preferred to add these f acld, compounds to the dyestuff prior to standardization in or- 8'ammO'1-I1aPhth01-3,'6-d15111f0I11c acid,

der to produce the novel dyestutf composition of the press'acetylamino-1-11aPhth01-3,G-diSUIfOIIiC d, ent invention which has a softer physical form and which 8-amino-1-naphthol-5,7-disulfonic acid, dissolves more readily in the dyebath. 8-chloro-1-naphthol-3,6-disulfonic acid.

The amount of diethylene triamine employed is also critical. If less than of diethylene trimine on the weight of dye is employed, there is practically no improvement in graniting. If more than 20% is employed, the product does not dry properly. Thus, 520% on the weight of dye is the critical amount.

In the preferred embodiment of the present invention the novel dyestuff composition thereof is formulated by mixing the dyestuff, preferably in the form of a dye paste taken directly from a filter press with about 5 up to 20% of diethylene triamine based on the weight of the dyestuif and also l030% based on the weight of the dyestuff of a material selected from the group consisting of (A) hexamethylene tetramine and (B) dialkali metal 4 Dyeing on paper 200 mg. of each of the dry colors thus obtained was then mixed into 300 g. of bleached sulfite pulp (10% strength). After mixing well as in the beater, it was allowed to stand for minutes and 1000 cc. of water at 40 F. was then added with agitation. After one minute, 2% of rosin size (1.7% solution) on the weight of the dry pulp Was added and then after agitation for one minute, 2 /2% of alum (1.5% solution) was added. After agitating for 15 minutes, the pulp was made into a hand sample of paper on a screen. The particular dyestuffs employed and the shade on paper is shown in the following table:

TABLE I Tetrazo Coupler Metal Shade on paper Formulation:

1 Dianisidine. 8-amin0-l-naphthol-3,6-disulfonlc aci l Cu Blue. 2.. d S-amino-l-naphthol-5,7-disulfonic acid- Cu Do. 3., .d0 S-anilino-l-naphthol-esultonie acid Cu Greenish blue. 4. do. G-amino-l-naphtliol-3,5-disultonic acid.-- Cu Blue. 5. do. 7-amino-1-naphth0l-3-sultonic acid.. Cu Blue-gray. 6. do 1-naplitl1ol-3,G-disulfonic acid Cu Grcenish blue. 7. do. 8-amino-l-naphthol-s-sultonic acid. Cu Do. 8. .do 6anilino-1-naphthol-B-sullonie acid Cu Blue. 9 (lo (l'amino-l-naphthol-B-sulfonie acid Cu D0.

phosphate, or mixture of (A) and (B). Water or other inert solvent is preferably added in such an amount as to form a slurry for easy mixing. After mixing well, the paste may be used as such for dyeing paper, but preferably is dried in any suitable manner such as by spray drying, drum drying or oven drying. The dried material is then preferably standardized in known manner using the usual standardizing agents such as sodium sulfate, dextrin, Tamol, urea, sugar. The product thus obtained is in a soft physical form which dissolves quite readily in the paper pulp. It also shows little or no graniting when dyed on paper in contrast to such other formulations, and a further advantage is that the dyestuff in this formulation is relatively insensitive to alum, frequently used for sizing paper.

While it is preferred to prepare the novel dyestulf composition of the present invention containing both this type of dyestuff and diethylene triamine and also preferably hexamethylene tetramine and/ or dialkali metal phosphate and add this to the dyebath (paper pulp), it will be understood that many of the advantages of the present invention may be obtained by adding the diethylene triamine and also preferably the dialkali metal phosphate to the dyebath (paper pulp) either before or after the dyestulf is added thereto. Especially in heavy dyeings, hexamethylene tetramine is preferred to the dialkali metal phosphate as the dialkali metal phosphate interferes with the size. The hexamethylene tetramine may be used without the dialkali metal phosphate, or in admixture in any proportion up to and including only the dialkali metal phosphate.

EXAMPLE 1 Preparation of dye composition A series of 9 dyestuif formulations were prepared by slurrying 85 parts by weight of the dyestuif presscake obtained by coupling one molar proportion of tetrazotized dianisidine with two molar proportions of each of the couplers shown in the accompanying Table I and coppering in the usual manner, with 10 parts of diethylene triamine, parts of disodium phosphate and a small amount of water to facilitate mixing. After the material was mixed well, it Was spray dried. 75 parts by weight of this dried material was then mixed with 23 parts of dex trin to standardize the same, 1 part of Twitchell oil and 1 part of antifoam agent. The product is a soft, powdery material having a light appearance.

Each of the dyeings thus obtained showed essentially no graniting as contrasted with a control dyeing using the same formulations and the same conditions but without the diethylene triamine and the disodium phosphate which showed considerable graniting. Also, the control dyeings were redder and duller than the dyeings obtained with the process of this invention.

Essentially the same results were obtained when disodium phosphate in the above formulations is replaced with equivalent amounts of either dipotassium phosphate or dilithium phosphate.

EXAMPLE 2 In order to better illustrate the decreased sensitivity to alum of the dye compositions of the present invention, the following experiment was carried out. It is to be noted that in the above examples the dye was on the fiber prior to treatment by alum, and thus, in a way protected from the alum. The dyeings employing the formulations of Example 1 were greener and brighter than the corresponding standard or control dyeing, but this difference was nowhere nearly as pronounced as in the case where the pulp is treated with alum first and then with dye so that the dye is not protected from the alum by combination with the fiber.

In carrying out this experiment, 300 g. of bleached sulfite pulp (10% pulp) is agitated with 2% rosin size (1.7% solution) on the Weight of the dry pulp for 1 minute, then with 2 /2% alum (1.5% solution) on the weight of the dry pulp for 1 minute, and then with 200 mg. of color for 15 minutes, and then made into a hand sample.

Standard or control dyeings made without diethylene triamine and disodium phosphate showed considerable graniting in contrast to the dyeing made with the formulations of Example 1 according to this method. Also, the dyeings made employing the formulations of Example 1 were greener and brighter.

However, these dyeings were less green and duller than those of Example 1, thus demonstrating the sensitivity of the dye to alum, but at the same time also demonstrating the ability of the diethylene triamine to reduce alum sensitivity.

EXAMPLE 3 parts of the blue dyestutf obtained by coupling approximately 2 moles of S-amino-1-naphthol-3,6-disulfonic acid with 1 mole of dianisidine tetrazo and copper (C.I. 24400) in the form of the presscake was slurried with 10 parts of diethylene triamine and a small amount of water to facilitate mixing. After the material was mixed well, it was spray dried. It was then finished in the manner of Example 1 to produce a soft powder. It was then! applied to bleached sulfite pulp in the manner of Example 1. There was essentially no graniting.

EXAMPLE 4 Example 3 was prepared with the exception that 12.5 parts of hexamethylene tetramine and 12.5 parts of disodium phosphate were employed instead of the 25 parts of hexamethylene tetramine. The results were commensurate.

While in the foregoing examples the novel dyestuff composition of the present invention has been added to the paper pulp as a dry powder, it will be understood that if desired, the dyestuff composition can be metered into the paper pulp. It has been found that the aqueous solutions of the dyestuif compositions of this invention are quite stable, whether originally prepared in the form employing the moist dyestuff presscake or prepared before in the form employing the moist dyestuff presscake or prepared before use by dissolving the dyestuif compositions of the foregoing examples in water. The following examples illustrate preferred embodiments of aqueous solutions encompassed in the present invention.

EXAMPLES 5-7 The following formulations were prepared:

Dyestufi of Example 3 (C. I. 24400), parts 100 100 100 Diethylene triamine 10 10 10 Hexamethylene tetramine 15 Triethylene tetramine 1 ater 74 6 Example 6 with practically no graniting. However, the shade shifted slightly to the redder side.

It will be understood that the foregoing examples are illustrative of the preferred embodiments of the present invention and various modifications will suggest themselves to those skilled in the art. Thus, in the examples the dyestulf was incorporated into the paper pulp so that in effect the pulp was the dyebath. It will be understood that if desired, the paper may be dyed after the web is formed by passing the Web through a separate dyebath containing the dyestuff composition of this invention, or by wetting the web with an aqueous solution (dyebath) of a dyestuff of the composition such as spraying or rollercoating and the like.

I claim:

1. The process of dyeing paper comprises dyeing the paper in a dyebath containing a composition consisting essentially of about parts by weight of dyestuif of formula:

O-Gu-O O-Cu-O s wherein n is 1-2, and X is hydrogen, chlorine or NHR, wherein R is hydrogen, lower alkyl, benzyl, aryl or acyl, and about 5 to 20 parts by weight of diethylene triamine.

2. The process as defined in claim 1 wherein the dyestuif composition contains about 10 to 30 parts by weight of a material selected from the group consisting of (A) hexamethylene tetramine and (B) dialkali metal phosphate and mixtures of (A) and (B).

3. The process as defined in claim 1 wherein the dyestuif composition contains about 10 to 30 parts by weight of hexamethylene tetramine.

4. The process as defined in claim 1 wherein the dyestuif composition contains about 10 to 30 parts by weight of dialkali metal phosphate per 100 parts of dyestuif.

References Cited UNITED STATES PATENTS 464,135 12/1891 Hoffman 260-182 1,984,096 12/ 1934 Straub 8-42 XR 2,092,429 9/1937 Straub et al. 8-42 2,492,702 12/ 1949 Neubart et a1 162-162 2,835,663 5/1958 Benz 8-42 DONALD LEVY, Primary Examiner US. Cl. X.R. 

